Preparation of hydrolyzable titanium solutions



Patented Oct. 26, 1948 PREPARATION OF HYDROLYZABLE TITANIUM SOLUTIONS Carl Marcus Olson, Oak Ridge, Tenn, assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Applica ion June 1, 1944, Serial No. 538,339

12 Claims. 01. 23-202) This invention relates to novel methods for preparing titanium salt solutions for hydrolysis and to the production of improved hydrolysis precipitates therefrom. More particularly, it relates to the preparation in increased yields of hydrous titanium-oxygen compounds by hydrolytic precl'pitation from acid solutions of titanium in order to obtain, as a final product, an improved type of anatase or rutile pigment.

This application is a continuation-in-part of my copending application Serial No. 355,601, filed September 6, 1940, now abandoned.

As is known, titanium oxide pigments useful commercially in coating compositions, such as paints, enamels, etc., may be produced by calcining the precipitate resulting from the hydrolysis of a titanium salt solution, such as a sulfate, chloride, nitrate, etc. Thus, a titanium sulfate solution may be prepared by dissolving ilmenite or other titaniferous ores by sulfuric acid attack. The resulting crude sulfate solution is clarified and a portion of the iron is removed as crystalline copperas by reduction followed by concentration and cooling. The final solution may contain up to or in excess of 250 grams of TiO2 per liter as a dissolved basic sulfate, about 50 g. of iron, from about 175 to 260 g. of free sulfuric acid, and varying smaller quantities of other metals. These titanium liquors, which are very dark in appearance, after prolonged boiling following nucleation (provided certain acid concentrations are maintained), precipitate a very white, hydrated titanium oxide. After careful Washing to remove dissolved metals, and suitable calcination and processing in accordance with well-known procedures, a fully-developed T102 pigment results as a final product.

When relatively high acid and titanium concentrations prevail in the solution subjected to hydrolysis, relatively low yields (below 90%) of T102 result. Relatively dilute solutions, on the other hand, increase the yield to some extent, but their use incurs an undesired sacrifice in product whiteness and filterability. In early T102 manufacture, yields of from about 70 to 90% had to be tolerated to obtain a product of passable color. To increase the yield to about 95% or above and facilitate precipitation of titanium from fairly strong or concentrated solutions and at the same time procure a product of good whiteness, it has been proposed to variously treat the titanium salt solution prior to hydrolysis, An outstandingly useful improvement process of this type contemplates intermingling or mixing the titanium liquor while at elevated temperatures, with a relatively minor quantity of water and subsequently raising the temperature of the mixture to boiling to induce TiOz precipitation. Admixture of the warm solution with the water produces a colloidal hydrous titanium oxide compound which acts as a beneficial nucleating or seeding agent in the hydrolysis. Another useful process involves the addition of a suspension of relatively fine, practically colloidal, hydrous titanium oxide to the hydrolysis solution as a nucleating material, said material having been previously prepared by neutralizing a portion of the hydrolyzable titanium liquor to a particular pH value. I

Other less advantageous proposals exist, th

purported object of which is to increase precipitate yields from seeded liquors. In one such process, water is added to the titanium solution while the latter is undergoing hydrolysis, the addition being efiected either continuously or in equal increments throughout the hydrolysis, or after the major portion of the titanium has been precipitated. Another proposes to add to the titanium liquor a large amount of a dilute solution of an organic acid, either alone or in admixture with phosphoric acid, and while elevated temperatures are maintained. These dilution methods are disadvantageous because the color and filterability characteristics of the final product become impaired to an adverse extent. Furthermore, water addition during hydrolysis necessitates interruption of the boiling or hydrolysis operation, the cooling of the solution prior to e-iiecting water addition, and the reheating of the resulting mixture. Aside from the undesirable effect upon product quality, it is obvious that hydrolysis interruption and cooling render this type of process quite unattractive from an economical and commercial standpoint. In addition, the physical nature of the fine particles precipitated in such processes, especially methods involving organic acid treatment, tends to impede the flow of Water through the filter cake causing Whatever colored impurities which are present to become strongly adsorbed upon or held by the precipitate. As a consequence, it is imperative that thorough,

repeated and prolonged washing operations be resorted to in such processes if a pigment of good whiteness is desired. Finally, due to its physical character, a considerable precipitate loss is incurred during washing and filtration because of the decided tendency of the pr p o p through usual filter media.

It has been found that the disadvantages encountered in such prior procedures may be effectively remedied. and it is, accordingly, among the objects of. t1[1is invention to overcomethese disadvantages and to provide novel methods for attaining such desired results. It is among the particular objects of this invention to provide,a method for preparing titanium salt solutions for hydrolysis from which one may ureadily procure improved Ti02 hydrolysates in increased, high yields, e. g., of approximately,98% orh m 110 provide a process from which .said high ,yields result while normal good whitenesmand ,other essential pigment properties are retained and preserved to provide a hydrolyzable titanium solution which will afford production of a precipitate having both improved whiteness and filterability characteristics with relatively complete reistanwtQwards loss. during filtration and washin ,to improve thefilterability of TiOzhrecipitates and espec a l ut by a east 50 a tofn lovide .a process from which these increased yields of high quality precipitate can be ob- .tai d u on h d ol s s of r at e y o cen at d titani m s l ls utivn es ec a ly titanium sulfate. I'lfhese and other objects are attainable in this invention which comprises, prior to hydrolysis andafterdesired nucleation and colloidal enrichment ,of a relatively concentrated titanium, salt selut onsadmixins a di ue wi a so u o in :sufilcientuuantity to render the same substanrt allv dilute in charact and then hyd o yzins trieiesutnam x re- Mere pe ifical t nventionwmp is ed.- ing a relatively concentrated acid solution of titanium, such as the sulfate, chloride, nitrate, w h n ne l ss thee b ta t lv 8 1 T O perliter hea the resulting seeded solution to increase ,the colloidal ,content thereof, thereafter m x n with said soluti n. but with t p ci ins substantial.amcuntsn -fi erabl pr ipitate, a quantity of adiluent suificient to reduce the 'IiOz concentration ,of said solution to not .in excess of substantially lGOgrams per liter, and than hydrqlyzing' the resulting ,dilutedmixture at an elevated temperature until substantlallycompletelrrecipitationof titanium is ,efiected.

,I n one preferred embodiment, the invention .pomprises preparing a concentrated, seededtitan'iumlsulfate-solution having .a T102 concentration rangingfrornsubstantially .190 lid-225 ll msp liter a d a factorof acidityof from about 50 to 0, '.heating said solution for a relatively short .period ,of time at temperatures ranging from substantiallydfl to 100 -C., in order to enrich the colloidal content of said solution, thereupon rapidly mixinga hot diluent'with said solution to decrease the TiGz concentration thereof .to .helOW SflbStantiaHy 150g. perli ter or about .145 g. per liter, effecting said rapid admixture prior to formation of la filterable precipitate in saidftitasenate solution, and then heating the resulting diluted system at temperatures ranging from substantially 100 .0. to the boiling point .the're o i",. t0 il febipitate from substantially 9 2 to Q9.%, of ,the'titariiun present.

'yvhile theinventicn is generally applicable to all types of hydrolyzable titanium salt solutions, and particularly to those referred to, it will be illustratively described in connection with one preferred adaptation thereof, involving the treatment of a titanium sulfate solution. These hydrolyzable solutions may be conveniently pre pared by initially attacking a titaniferous ore or titanium-containing material, such as ilmenite, with a mineral acid, particularly sulfuric acid. Suitable methods for preparing said sulfate solutionsinclude ,those setforth U. S. Patent 1,504,659 to'Blumenield. The resultingmass or reaction product from such acid attack is dissolved in water or dilute sulfuric acid, and the solution thus obtained is subjected to the usual purification, clarification and concentration treatments to obtain a relatively concentrated solution containing not less than substantially ,toiBlumenfeld or Reissue Patent 1.3,790to Meeklenburg. Forinstance, the nuclei may be formed th e sqlution by gradually adding the relatively concentrated titanium sulfate solution to water while the latter is maintained at an elevated temperature; or thenuclei maybe formed by adding a small volume of the liquor to a larger volume of water held at such elevated temperature, following which filtration is bad to remove sulfate ionsfland ,the resulting nuclei is incorporated in the solution. The resulting mixture or suspension is then heated, for a relatively short period of time but less than that which would result in any/substantial formation of a filterable precipitatawhereby desirable enrichment is had of the colloidal TiQ2 content of said solution. The temperature employed in effecting such enrichment belowthe substantial boiling point of the solution and preferably ranges from about to C. The time expended in heating to eliect enrichment will depend upon the temperature, concentration, etc, of the liquor, but usually ranges from about 10 minutes to 1 hour. Whatever temperature or extent of heating is resorted to, heat treatment is interrupted immediately priorto the time at which the solution indicates it issuSce tible of substantially immediate change to a creamecolored appearance which is a warning or indication that a white hydrolyzing titanium oxide, flocculating into particles of filterable dimension, is imminent. That is. it is critical andessential .inthe invention, in procuring .optimum results, that the heating step to effect colloidal enrichmentof the titanium solution shall bearrested upon an increase in solution turbidity being noted and upon change of the solution color, successively, from-black to olive green or steel gray, and to suspend said heating immediately prior to the moment that definite indications appear that the solution is ready to change, flocculation, from a state where substantially no precipitation is observable to a coagulated condition-Which will provide a substantially filterable suspension of hydrolysate in the sulfuric acid media. When this stage is reached and rhevating ris interrupted, a suitable quantity of a ,diluent, such as pure water or a very dilute sul- ,furic acid solution containing trivalent titanium maintained, preferably, at an elevated tempera- -'ture approximating substantially the temperature "of the solution under treatment, is caused to be "rapidly admixed with and dispersed throughout the colloidally enriched solution. The amount of diluent employed in effecting said diluent may rangefrom substantially 5 to 25% by volume of the solution undergoing treatment and preferably comprises from about to thereof. While these amounts are suggested, it will be obvious thatthe amount employed will largely depend upon the character and Ti02 concentration of the solution under treatment. In any event, the amount of diluent employed must be sufficient to reduce the T102 concentration of the solution from-180 g. per liter or higher to not in excess of about 160 g. or to as low as substantially 120 grams. Preferably, however, the secondary dilution is so conducted that the solution which is finally subjected to actual hydrolysis has a T102 concentration ranging from substantially 140 to 150 g. per liter. After suitable treatment, the resulting diluted system is hydrolyzed at temperatures from substantially 100 C. to the boiling point thereof, whereby precipitation in excess of substantially 95% and about 98 or 99% of the titanium present is procured. Preferably, said hydrolysis is conducted in accordance with the procedures described in said Reissue Patent 18,854 or 18,790. The resulting hydrolysate will be found to exhibit improved color or whiteness characteristics, as well as improved and desired filterability properties. The precipitate recovered from the hydrolysis is washed, calcined, ground, dried and finished in the usual manner,

a final TiOz product being obtained possessing desired increased whiteness, tinting strength, hiding power, fine, uniform particle size, as well as other essential pigment properties.

To a more complete understanding of the invention, the following specific examples are given which are not to be considered as in limitation but .merely in illustration of the invention:

Example I I A titanium sulfate solution was prepared by dissolving ilmenite by means of strong sulfuric acid and subsequently treating by known chemical methods giving a low iron, mud-free solution containing about 260 grams T102 per liter and having a factor of acidity of 75. About 1% of seed based on T102 content, prepared by neu- 'tralizing 100 ml. of the solution to pH 4 in accordance with the process of U. S. Reissue Patent 18,790, was added to ten liters of the above solution. 0n heating at 90 C. for minutes no filterable titanium compounds were present. Upon noting a rapid increase in color change, enough water at 90 C'. to reducethe dissolved Ti02 concentration to 145 grams per liter was added and the temperature raised to boiling. Immediately after the dilution was completed the precipitation of white hydrous titanium dioxide was apparent. After boiling for three hours the suspension was cooled somewhat and filtered. filtration was readily accomplished with less solid material escaping with the filtrate than is observed in other methods of preparing TiOz. After washing, calcining, wet grinding, drying and dry grinding, in accordance with regular practice the resulting pigment had superior color and tinting strength, and other properties fully equal to. products of prior art processes. A yield of 98% of theoretical was obtained. The filtrate, diluted somewhat by the first portion of the washwater contained about 250 grams per liter of free H2804 Example II The process described in Example I was re-- peated, but instead of diluting the seeded liquor to 145 grams T102 per liter, dilution to 160 grams per liter was employed. As a result a normal yield of about 94 to 95% was obtained, but the product had excellent filterability and improved whiteness characteristics.

Example III A complex nuclei suspension was prepared in accordance with U. S. Patent 2,342,483, by :blending equal amounts of (a) A yield-inducing hydrolysis nuclei suspension, prepared by adding one volume of a titanium sulfate solution containing 150 grams per liter of TiOz to two volumes of water, adding sulficient caustic soda solution thereto to bring the pH value to 2.7 and provide a suspension containing 30 grams per liter of T102, raising the temperature to 80 C. and maintaining at that temperature for 30 minutes, after which the seed Was cooled, filtered and reslurried to grams per liter of T102, and

(b) A rutile-inducing nuclei suspension, prepared by adding one volume of titanium tetrachloride solution containing grams per liter of TiO with stirring to one volume of water containing 128 grams of NaOI-I per liter, heating the resulting mixture to C. for 30 minutes and then cooling and neutralizing to '7 pH by addition of dilute sodium hydroxide solution, washing the precipitate free of chlorides and then reslurrying in water to provide a suspension containing '75 grams per liter of T102.

Ten volumes of this complex seed suspension, containing 75 grams of Ti02 per liter, were added to 125 volumes of a titanium sulfate solution containing 200 grams per liter of T102, 60 grams per liter of iron, and 500 grams per liter of sulfuric acid at a temperature of 80 C. The tem perature of the seeded solution, after incorporation of the seed by stirring, was raised at the rate of of a degree per minute. When a temperature of about 100 C.-102 C. and the graying point (where the color turns from a clear black to gray) was reached, the heating was interrupted and 50 volumes of water were added after which the heating was continued with stirring. The solution was then boiled for three hours. A 96% yield of a Ti02 readily filterable hydrolysate, adapted to convert to rutile on calcination below 1000 C. was obtained. This precipitate, after separation from acid and impurities, was calcined in the presence of a small amount of alkali metal salt in accordance with U. S. Patent 1,892,693 at a temperature of 950 C. to give a completely converted rutile product of high strength, excellent color, hiding power and undertone.

The above procedure was repeated, except that the hydrolysis solution was not diluted with water as was done above at a temperature of 101 C. The hydrolysis product was compared for filtration properties as were the properties of the final pigment with that obtained employing the dilution procedure. The tests revealed that hydrolysis with dilution gave a more easily filtered product and that filtration capacity of the plant would be increased about 60%. The yield on hydrolysis without dilution was 94.2% for the three hours boiling time and only conversion to rutile was obtained under the same cal- :cination icondit-ions. @Although :the wtinting two .typesof hydrolysate and ;final pigment are rmore particularly shown in the following table :(the color and tinting -;str ength values having :heenzdetermined in;accordance-with the methods referred to in U. s. Patent ,No.';2,2'13,;542)

In adapting the invention, the seeded titanium "sulfate or other salt solution may be prepared in accordance with any known or desired procedure.

Likewisa'the invention is usefully adaptable to the production of anatase :or'rutile pigments as well as to the production of various types of hydrolysates from whence such pigments are derived. It is particularly useful in hydrolysis methods designed toproduce anatase forms of precipitate which will convert to rutile under the calcination a temperatures normally used in anatase pigment manufacture, and whether such precipitates result by reason of a particular typeof seeding agent or otherwise. The solutions used herein need not be-especially pure in character, but may contain the usual impurities resulting from the attack of titanium ores with the corresponding acids. The methods of the aforesaid Mecklenburg and Blumenfeld patents are'very satisfactory and therefore'preferred. In practicing the Blumenfeld type of seeding, wherein the nucleationis accomplished by the interdiffusionor mixing of the titanium solution with a diluent, it has been foundpreferable toadjust the concentration of the original titanium solution so that after seeding is accomplished, the T102 concentration is not less than about 190 to 200 g. per liter.

While lesser concentrations may be used, they will be found lessadvantageous, especially because of the increased danger from the formation of a filterahle'precipitate during the enrichment period. Again, while said enrichmentperiod may be as short as, say 1-0 minutes, it will be found preferable to resort to longer periods through employment of more concentrated solutions,

therebyallowing ample time for the accomplishment of desired -complete dilution beforethe appearance of any lilterable precipitate. As already noted, the addition of water to thehot liquor after the appearance of a precipitate endangers thegood whiteness of the product and an undesired cooling of the'solution before adding-water will be necessary in an attempt to safeguard color quality. By dilution prior to any substantial precipitation, however, interruption of the heatingbecomes entirely unnecessary.

As already noted, the secondary dilution may be accomplished with agents other than relatively pure'water, such as dilute sulfuric acid, or with liquors derived from other sources such as the wash waters from titanium precipitate purification operations. Preferably, dilution of the seed- ;ed solution is effected with .a hot diluent because itsuse is more advantageous :and beneficial and in :addition :save'stimein bringing about the de not unusual.

.-sired precipitation. However, it .;is 'withim'the scope of the invention to employ arrelatively'scold fected before undesired precipitation ,ofi'the xby- .:drolysate occurs. Either liquid may'be mixed with the other or both {may ,-be-;simult.aneously commingled, as in aventuritmixet, iandlsimilar continuous mixing devices. .Also, the degree :of dilution may'vary, as .noted zabova and in factithe degree of'dilution may be deliberately controlled in order to achieve either an improvement :in color and filterability with a normal zyie'ld of hydrolysate or an increased -yieldand improved filter-ability with normal color. Also; the proportion .of free acid'in the solution priorrto hydrolysis may vary considerably althoughwlt ;is preferred to employ solutions havingyalues for the factor ,of acidity which lie betweenxsubstantially :50and 100.

.As will be evident, the instantinvention'constitutes a clear departure from :and advancement over prior methods and by the feature ,ofqcompleting dilution beforeprecipit-ation occurs,'ta-voids the disadvantages of the post-precipitation dilu- .tion processes and enables the production of an improved type of precipitate as 'wellasfinal-pl ment. Thus, an increase ,in yield of a't least 21120 4% or higher is readily effected while maintaining normally good color of product; furthenasan accompaniment of such increase in yield, a decided improvement is had inboth color and'filterability :of the precipitate. The improvement in ufilterability is most notable in my process,-.since:it'wi1l be found toadvantageously afford a ready increase of at least 50% in this respect..alone, 'with filterability increases above 70% or'1'00,% being Again, .the novel method :of dilution of the present invention has "an advantage-over others resulting from the improved filterability which makes possible a sham cut between the mother liquors and washings. This factor is particularly valuable in maintaining a :reasonably high concentration-oi the mother liquor. making it more adaptable for recovery or reuse than highly diluted solutions. Another advantage arising from improved filterability of theprecipitate-ob tainable herein is the considerable time saving which is efifected in the necessary filteringand washing operations. Further, ash'orter heating or boiling time is required in the process to obtain said desiredhigh yields, thereby effecting a considerable economy in TiOz pigment pro- .duction.

The exact manner'by which the unexpected results attainable in this invention arise -is not completely known and therefore the invention should not be considered as "limited toqany particular theory. One explanation thereof :maybe given as follows:

During-the hydrolysis .of titanium solutions the free acid concentration gradually increases .due to its liberation from titanium. Thisis-shown by the following chemical equation illustrating the hydrolysis of titanyl sulfate:

This increasing acid concentration, in '-'a'ccordgreater yields by diluting the solutions are,

therefore, logical'and well understood, However,

his well known that the addition of water to these systems during precipitation impairs the whiteness of the product as also does excessive dilution prior to precipitation. This appears to arise because the colored ions or hydrous oxides of such metals as Fe, Cr, V, etc., are less readily adsorbed by the titanium oxide under high acidic conditions. When water or weak solutions are added to the hydrolyzing system after precipitation has begun, it is practically impossible to avoid local-zones of high dilution and any material precipitated therein is contaminated. Consequently, those who have practiced dilution during precipitation have found it necessary to stop the precipitation by cooling before adding water or to add other agents. Due to the time lag in starting and stopping the hydrolysis reaction, it is apparently not practical to completely prevent precipitation during dilution according to prior art methods, consequently no improvements in quality have been observed. In the instant invention, by completing the dilution beforeprecipitation begins, these diificulties are effectively avoided. When the concentration of the titanium solution is sufiiciently great, no precipitation even in the presence of seed will occur or prolonged boiling. At somewhat lesser concentrations a heating period varying, from several minutes to an hour or two, is necessary to cause precipitation. It is during this, perioid, prior to precipitation, but subsequent to the seeding of the solution, that the dilution according to this invention is accomplished. Since the diluent is thoroughly mixed with the solution befor precipitation begins no precipitate is formed under conditions of local high dilution and this accounts for the improved quality obtained, or

the extraordinarily high yield obtained without lowering the color quality. This new method of dilution also tends to improve the filterability of the product. It is not known just why this occurs, but presumably the hydrolyzed titanium dioxide, which is of a fiocculent nature, is formed in closer, more granular flocs which permits the eaSy passage of mother liquor and also avoids the loss of product by the escape of unassociated or dispersed primary particles through the filter medium.

The term free acid, as used herein, is meant to refer to the excess of acid over and above that chemically combined with the basic constituents of the solution, such as titanium, iron and other metals. In calculating values for free acid, 1 mol of acid is asumed to be combined with each mol of titanium. Factor of acidity, also desig-' nated F. A., is the ratio of free acid to acid combined with titanium in the liquor multiplied by 100. Thus,

Free acid Acid combined with titanium hydrolysis of titanium solutions, the formation of a filterable precipitate is marked by the development of a turbidity or milkiness in the solution. By the term good filterability is meant a satisfactory retention of the solids by the filter media and ready passageof the motor liquor in 10 washings through the filter cake in an evenly distributed manner.

I claim as my invention:

1. A method for obtaining an improved hydrolysate from a concentrated, hydrolyzable titanium salt solution having not less than 180 g./l. TiOz and containing seed nuclei adapted to accelerate its hydrolysis, comprising heating said solution after it has been nucleated to increaseiits, colloidal T102 content, upon an increase in turbidity of said solution taking place as a result of said heating but prior to formation of a substantially filterable TiOz precipitate in the solution, interrupting said heat treatment and thereupon mixing a sufiicient quantity of a diluent with the colloidally enriched solution to reduce its T102 concentration to below 160 g./1., and then heating the resulting diluted titanium solution to efiect its hydrolysis and precipitate said improved T102 hydrolysate.

2. A method for obtaining an improved hydrolysate from a concentrated, hydrolyzable titanium sulfate solution having not less than 180 g./l. T102 and previously seeded with nuclei to accelerate its subsequent hydrolysis, comprising after nucleation of said solution heating the same to increase its colloidal T102 content, upon an increase'in the turbidity of said solution taking place as a result of said heating but prior to formation in said solution of a substantiallyfilterable T102 precipitate, interrupting said heat treatment and thereupon mixing a sumcient quantity of a diluent with the resulting colloidally enriched solution to reduce its TiOz concentration to below 160 g./l., and then heating the diluted titanium solution thus obtained to efiect its hydrolysis and precipitate said improved T102 hydrolysate.

3. A method for obtaining an improved hydrolysate from a relatively concentrated titanium salt solution containing at least 180 g. T102 per liter and which solution has been previously seeded with TiOz nuclei adapted to accelerate its subsequent hydrolysis, comprising after nucleation of said solution subjecting the same to heat treatment to build up its colloidal TiOz content, upon an increase in the turbidity of said solution taking place as a result of said heating and prior to formation in said solution ofa substantially filterable TiOz precipitate, interrupt ing said heating operation and then incorporating a suificient quantity of a diluent in the resulting colloidally enriched solution as will reduce its TiOz concentration to from substantially tof g./1., and then heating the resulting diluted solution to effect its hydrolysis'and precipitate said improved T102 hydrolysate. v,

. 4. A method for obtaining an improved hydrolysate from a relatively concentrated titanium sulfate solution containing at least g, T102 per liter, which solution previously has been treated to provide seeding nuclei therein adapted to accelerate its subsequent hydrolysis, comprising following nucleation of said solution, subjecting the same to heat treatment to build up its colloidal T102 content, upon 'an'increase in the turbidity of said solution being notedfroln said heating and prior to formation of a sub stantially filterable TiO2 precipitate therein, interrupting said heat treatment, and then incorporating a sufficient quantity of a hot diluent in the resulting colloidally enriched solution where by its T102 concentration is reduced to from substantially I20 to 160 g./l.', and then heating the resulting diluted solution to hydrolyze the same 1 l and precipitate said improved, TiOz hydrolysate. 5. A method for obtaining an improved hydrolysate from a relatively concentratedtitanium chloride solution containing at least 180 g. TiOz per liter and previously seeded with T102 nuclei adapted to accelerate its subsequent hydrolysis, comprising following nucleation of said solution subjecting the same to heat treatment to build up its colloidal T102 content,;upon an increase in the turbidity of said solution being noted as a result of said heating but prior to formation therein of a substantially filterable TiOz precipitate, interrupting said heating operation, thence incorporating a sufiicient quantity of a diluent in the colloidally enriched solution to reduce its TiOz concentration to from substantially 120 to 160 g./l., and then heating the resulting diluted solution to hydrolyze the same and precipitate said improved T102 hydrolysate.

6. A method for obtaining an improved hydrolysate from a relatively concentrated. titanium nitrate solution containing at least 180 g. TiOz perliter and previously seeded with TiOz nuclei adapted to accelerate its subsequent hydrolysis, comprising following nucleation of said solution subjecting it to heat treatment to, build up its colloidal T102 content, upon an increase in the turbidity ofsaid solution being noted as a result of said heating but prior toformation therein of a substantially filterable T102 precipitate, in-

terrupting said heating operation, then incorporating a sufiicient quantity of a diluent in the colloidally enriched solution to reduce its TiO2 concentration to from substantially 120 to 160 g./l., and then heating the resulting diluted solution to hydrolyze the same and precipitate said improved TiOz hydrolysate.

'7. A method for treating a nucleated, hydrolyz able, relatively concentrated titanium salt solution containing at least 180 g. TiOz per liter to improve the character and yield of precipitate obtainable on hydrolysis, comprising priorto said hydrolysis and after nucleation of said solution through incorporating of seeding nuclei therein, heating the seeded solution: at a temperature rangingv from substantially Soto 100.? C. to. effect colloidal enriclunent thereof, interrupting said heat, treatment; upon a rapid change; taking place inthe turbidity of the solution being treated, andthen prior to precipitation of a filterable precipia tate taking placaincorporating a hotv diluent in said solution in sumcient amount to reduce its T102 concentration to from substantially 120,- to. 160; g. per liter, and then hydrolyzing at an elevated temperature the resulting dilute solution.

8. A method for treating a nucleated, hydrolyzable and relatively concentrated titanium sulfate solution, containing at; least 180 g. TiOz per liter to improve the character and, yield of precipitateobtainable therefrom on hydrolysis comprising,

prior to said hydrolysis and after nucleation of said solution by incorporating seeding nuclei therein heating the seeded solution at a, tempera.-

ture ranging from substantially 80 to 710,0 C. to

colloidally enrich the same, interrupting said heating operation upon a rapid change taking place in the turbidity of-the solution under treat.- ment, and then prior to occurrence of precipitation of a filterable precipitate therfrom incorporatin hot water in'said solutionin sufficient amount to reduce its TiOz concentration to; from substantially-120 to 160 g. per liter, and then hydrolyzing at an elevated temperature the re sulting dilute solution.

.9. Amethod for-treating la nucleated, ydrolyzable and relatively concentrated titanium salt solution containing at least 180 g. T102 perliter to improve the character andyieldof .hydrolysate obtainable therefrom, comprising, prior to. by drolysis of said solution and after nucleation thereof by gradually mixing said concentrated titanium salt solution with a hot diluent, heating the nuclei-containing solution at a, temperature ranging from substantially -100 C. to colloidally enrich the same, arresting said heat treatment upon occurrence of a rapid change in solution color and turbidity, and then, prior to precipitation of a filterable precipitate therefrom, incorporating in said solution from substantially 5 to 25% by volume, based on the solution undergoing treatment, of a diluent to reduce the TiO2 concentration of said solution to from substantially to 160 g. per liter, and then hydrolyzing the resulting dilute solution. 7

10. A process for treating a nucleated, hydrolyzableand relatively concentrated titanium sulfate solution containing from substantially 190 to 225 g. TiOz per liter, and having a free acid factor ranging from about 50 to 100, to improve the character and yield of hydrolysate obtainable therefrom, comprising, subsequent to nucleation through gradual admixture of said concentrated titanium sulfate solution with a hot dilucut, and prior to hydrolysis thereof, heating said nucleated solution for a short period of time at a temperature ranging from substantially 80- 100 C. to effect colloidal enrichment thereof, interrupting said heating upon a rapid change in the color and turbidity of said solution taking place, thereupon but prior .to precipitation of a filterable precipitate, incorporating a hot diluent in said solution in sufficient quantity to reduce its TiOz concentration thereof to from substantially to g. per liter, and then hydrolyzing at an elevated temperature the resulting dilute solution.

11. A method for treating a nucleated, hydrolyzable, relatively concentrated titanium sulfate solution containing from substantially 190 to 225 g. T102 per liter, to improve the filterability characteristics of a precipitate obtain able therefrom on hydrolysis, comprising, prior to said hydrolysis and after nucleation ofsaid solution, by gradually adding the latter to a hot diluent, heating the said solution to a temperature ranging from substantially 80-100 C; to effect its colloidal enrichment, interrupting said heating upon a rapid change occurring in the color and turbidity of the said solution taking place, thereupon, but prior to the occurrence of any substantial precipitation of a filterable TiOz, precipitate from said solution, incorporating therein an amount of diluent therein ranging from substantially 5 to 25% by volume of the solution under treatment to reduce its T162 content to below g,./l. and above 120 g./l., and then hydrolyzing the resulting dilute solution at an elevated temperature.

12. A method for treating a nucleated, hydro lyzable, relatively concentrated titanium. sulfate solution containing from substantially to 225 g. TiOz per liter to improve the filterability characteristics of a T102 precipitate obtainable therefrom on hydrolysis, comprising, prior tohya drolysis and after nucleation of said solution, by gradually adding the latter to a hot diluent, heating the same at a temperature ranging from substantially 80-100 C. to effect its colloidal enrich!v ment, interrupting said heating upon a rapid change occurring in the. color and turbidity: 0t

13 the solution under treatment, thereupon, but prior to any substantial precipitation of a filterable T102 precipitate from said solution, incorporating an amount of diluent therein ranging from substantially 10 to 20% by volume of the solution under treatment, whereby its T102 concentration becomes reduced to from substantially 140 to 150 g. per liter, and then hydrolyzing the resulting dilute solution at an elevated temperature.

CARL MARCUS OLSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,851,487 Blumenfeld Mar. 29, 1932 5 Re. 13,854 Blumenfeld May 30, 1933 OTHER REFERENCES Gardner et al., Physical and Chemical Examination of Paints, varnishes, Lacquers, and

10 Colors, 10th edition, pp. 35-36. 

